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Chapter 3
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Shampoo and
Conditioner Science
Robert Y. Lochhead
University of Southern Mississippi
Introduction
Located within the hair follicle is a sebaceous gland that
continuously excretes an oily material, known as sebum, onto
the hair and scalp. This substance consists of compounds such as
fatty acids, hydrocarbons, and triglycerides, and serves as natures
conditioning treatmentproviding lubrication and surface
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Chapter 3
Surfactant Micelles
Relatively large aggregates form within solution just beyond
the concentration at which the surface becomes saturated with
surfactant.8 These aggregates are surfactant micelles in which
the hydrophobes are segregated within the core of the aggregate
and the hydrophilic groups are located on the surface where they
interact strongly with water.9 For a given system, micelles initially
form at the precise concentration at which the driving force for
surface adsorption becomes equal to the driving force for aggregate
formation. This driving force is the chemical potential of the
surfactant species. The lowest concentration at which micelles form
is named the critical micelle concentration (CMC). The aggregates are
large; for example, micelles of sodium dodecyl sulfate at the CMC
contain about 100 molecules and the thickness of the head group
layer is about 0.4 nm.10
Surfactant micelles have liquid centers. They effectively solubilize
hydrophobic substances only when the temperature of the system is
above the Krafft point. Krafft found this phenomenon in 1895, and
68 years later Shinoda explained that the Krafft point corresponds to
the melting point of the hydrated solid surfactant.11
Micelles have different shapes. The simplest shape is the
spherical micelle that was postulated by Hartley in 1936. The
shape of a micelle can be explained on the basis of the principle
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Eq. 1
Eq. 2
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Figure 8. Rod-like micelles can pack into hexagonal liquid crystal phase.
Chapter 3
Figure 10. In this mechanism the oil contact angle at the oil/water/fiber interface
steadily increases until it rolls up and floats off of the solid surface. This
mechanism was first reported by N. K. Adams.
The oil droplet is rolled up on the surface, and when the contact
angle reaches 180 degrees, the interfacial force that is holding it to
the surface is overcome by the wetting tension of the oil and aqueous
solutions on the fiber surface. Roll-up is favored by fibers that are
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Figure 11. In the roll-up mechanism, the detergent solution can be transported
to the fiber/oil interface along the fiber surface, through a permeable coating
on the fiber, or through the fiber itself.
Chapter 3
Figure 12. Emulsification can remove the soil if the interfacial tension between the
oily soil and the surfactant solution is low.
In the penetration mechanism of oily soil removal, surfactantrich phases penetrate the oil at the interface. This results in an
interfacial liquid crystalline phase that swells and is broken off
to reveal a fresh soil interface, and then the process is repeated
again and again.31 The penetration mechanism occurs with polar
soils and/or phase separated coacervates of nonionic surfactants
above the lower critical solution temperature (LCST). Spontaneous
emulsification, in the absence of detersive surfactant, has been
observed for non-polar-polar soil mixtures like sebum.32 The
penetration mechanism can occur with anionic surfactants that
form coacervate phases in the presence of calcium salts.33
Solubilization is the process of incorporating a water-insoluble
hydrophobic substance in the internal hydrophobic core of micelles.
Direct solubilization can occur in the presence of an excess of
surfactant micelles with respect to oily soil.34 The rate of exchange
of surfactant molecules between micelles is important because the
micelles must re-assemble around the soil to solubilize the soil by
encompassing it inside the micelle.
Foam/Lather
One essential attribute of a shampoo is its ability to produce
a rich lather or foam. The important elements of a foam are
the lamellae and the Plateau border. The micrograph in Figure
13 depicts these structural features of a foam. The lamellae are
stabilized by surfactants adsorbed at the air-water interface.
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Chapter 3
Solid Foams
Cationic conditioners
that would normally be
incompatible with liquid
shampoos can be delivered
from solid foams. Solid
foams also make it possible
to have one scent for the
solid and then to allow
a different fragrance to
bloom when the solid is
wetted by water.35 The
porous solids are made by
mixing the surfactants,
glycerin as a plasticizer,
and water in the presence
of a water-soluble polymer.
Figure 14 shows a solid
foam in which poly(vinyl
alcohol) is the water-soluble
polymer. After a heating
and mixing cycle, the
porous solid is formed by
aeration.
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Chapter 3
Enhancing Mildness
Isethionates are surfactants noted for their mildness to skin,
and for at least three decades, they have been the basis of non-soap
detergent bars such as Dove (Unilever). They have been making
inroads into shampoos based upon mildness claims. Moreover,
Unilever researchers discovered that the mildness can be enhanced
even further by including mildness benefit agents that can be
flocculated by cationic polymers present in the formulation and
delivered as flocs upon dilution of the formulation.36 The preferred
benefit agent in this case is petrolatum; the cationic polymers
are well known polymers like polyquaternium-10 and guar
hydroxypropyltrimonium chloride. This could form the basis of
shampoos that are mild to the skin.
Certain non-cross-linked linear acrylic copolymers can lower
the irritation potential of surfactants and provide products that are
clear and highly foaming.37 The preferred polymers interact with the
surfactant and effectively shifting the CMC to higher concentrations,
while lowering the critical aggregation concentrationthe latter
being the concentration at which the surfactant selectively interacts
with the polymer rather than adsorbing at the liquid surface
(Figure 15). It is postulated that free surfactant molecules and
91
Conditioning Shampoos
Todays conditioning shampoos are expected to confer wet-hair
attributes of hair softness and ease of wet-combing, and the dry hair
attributes of good cleansing efficacy, long-lasting moisturized feel,
and manageability with no greasy feel.
The origin of conditioning shampoos can be traced to the
balsam shampoos of the 1960s followed by the introduction of
polyquaternium-10 by Des Goddard38,39 in the 1970s and 1980s in
which he introduced the concept of polymer-surfactant complex
coacervates that phase-separate and deposit on the hair during
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Figure 16. A schematic phase diagram that explains the mechanism of coacervate
formation in 2-in-1 shampoos.
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Figure 17. Lamellar gel subjected to high shear rolls up into vesicles of gel phase that can
be used for conditioning. (Figure reproduced from US Patent Application 20110243870).
Chapter 3
Chapter 3
Conditioners
Conditioning of damaged hair is commonly achieved by
treatment with aqueous formulations that contain fatty alcohols,
cationic surfactants, and (optionally) silicones. These components
are considered to adsorb in a hydrophilic head-down, hydrophobic
tail-up conformation that confers hydrophobicity on the damaged
hydrophilic hair surface. The role of a conditioner is to confer sleek
lubricity and gloss on the hair. Conditioners are usually based
upon cationic surfactants, and they most often are in the form
of emulsions of multi-lamellar vesicles. Conditioners comprise a
primary cationic surfactant, a co-surfactant, and dissolved salt.
Conventional conditioner formulations are based upon lamellar
gels or emulsions using either ceto-stearyl trimethylammonium
chloride or distearyldimethylammonium chloride as cationic
surfactants and ceto-stearyl alcohol as co-surfactant.
As a primary surfactant, the vast majority of conventional
conditioners contain either cetyl/stearyl trimethylammonium
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Chapter 3
Conditioning Polymers
Cationic conditioning polymers are used to enhance the
conditioning properties, especially to mitigate the effects of extreme
processing that are experienced during hair-straightening. Cationic
polymeric conditioners can improve wet combability and ameliorate
electrostatic charging of the hair (manifested by flyaway).
Many cationic polymers have been developed for the purpose
of conferring conditioning properties on hair. In fact, there are
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Silicone Conditioners
Silicone quaternaries have long been known as hair conditioning
compounds.
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